JP2542117B2 - Method for producing silyl unsaturated carboxylate - Google Patents
Method for producing silyl unsaturated carboxylateInfo
- Publication number
- JP2542117B2 JP2542117B2 JP2280255A JP28025590A JP2542117B2 JP 2542117 B2 JP2542117 B2 JP 2542117B2 JP 2280255 A JP2280255 A JP 2280255A JP 28025590 A JP28025590 A JP 28025590A JP 2542117 B2 JP2542117 B2 JP 2542117B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- reaction
- acid
- carboxylic acid
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000007942 carboxylates Chemical class 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 title claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- -1 carboxylic acid silyl ester Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ISEIIPDWJVGTQS-UHFFFAOYSA-N tributylsilicon Chemical compound CCCC[Si](CCCC)CCCC ISEIIPDWJVGTQS-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000005046 Chlorosilane Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WEAZWKYSTGLBSQ-UHFFFAOYSA-N tributylsilyl 2-methylprop-2-enoate Chemical compound CCCC[Si](CCCC)(CCCC)OC(=O)C(C)=C WEAZWKYSTGLBSQ-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NQNRLCXPKYFOLR-UHFFFAOYSA-N CCCC[Si](CCCC)(CCCC)OC(=O)C(C)C Chemical compound CCCC[Si](CCCC)(CCCC)OC(=O)C(C)C NQNRLCXPKYFOLR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 2
- HVMNIRCQQXUXRP-UHFFFAOYSA-N triphenylsilyl prop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C=C)C1=CC=CC=C1 HVMNIRCQQXUXRP-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- FEGVSPGUHMGGBO-VOTSOKGWSA-N (E)-2-methoxycinnamic acid Chemical compound COC1=CC=CC=C1\C=C\C(O)=O FEGVSPGUHMGGBO-VOTSOKGWSA-N 0.000 description 1
- KFSQJVOLYQRELE-HWKANZROSA-N (e)-2-ethylbut-2-enoic acid Chemical compound CC\C(=C/C)C(O)=O KFSQJVOLYQRELE-HWKANZROSA-N 0.000 description 1
- XNCRUNXWPDJHGV-BQYQJAHWSA-N (e)-2-methyl-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(/C)=C/C1=CC=CC=C1 XNCRUNXWPDJHGV-BQYQJAHWSA-N 0.000 description 1
- PEXWJYDPDXUVSV-BQYQJAHWSA-N (e)-3-phenylbut-2-enoic acid Chemical compound OC(=O)\C=C(/C)C1=CC=CC=C1 PEXWJYDPDXUVSV-BQYQJAHWSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- FEGVSPGUHMGGBO-UHFFFAOYSA-N 2-methoxy cinnamic acid Natural products COC1=CC=CC=C1C=CC(O)=O FEGVSPGUHMGGBO-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QGPXSLBTWVMQMW-UHFFFAOYSA-N butyl(diethyl)silane Chemical compound CCCC[SiH](CC)CC QGPXSLBTWVMQMW-UHFFFAOYSA-N 0.000 description 1
- HXLVDKGPVGFXTH-UHFFFAOYSA-N butyl(dimethyl)silane Chemical compound CCCC[SiH](C)C HXLVDKGPVGFXTH-UHFFFAOYSA-N 0.000 description 1
- MNSBLWANOCYPMT-UHFFFAOYSA-N butyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](CCCC)C1=CC=CC=C1 MNSBLWANOCYPMT-UHFFFAOYSA-N 0.000 description 1
- PQBRRVGEMZBEOK-UHFFFAOYSA-N butyl-ethyl-methylsilane Chemical compound CCCC[SiH](C)CC PQBRRVGEMZBEOK-UHFFFAOYSA-N 0.000 description 1
- XUQLQANKZXCICL-UHFFFAOYSA-N butyl-ethyl-phenylsilane Chemical compound C(CCC)[SiH](C1=CC=CC=C1)CC XUQLQANKZXCICL-UHFFFAOYSA-N 0.000 description 1
- CKXWNASGWZZYEA-UHFFFAOYSA-N butyl-methyl-phenylsilane Chemical compound CCCC[SiH](C)c1ccccc1 CKXWNASGWZZYEA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- RSVCGWGXDUXRJI-UHFFFAOYSA-N dibutyl(ethyl)silicon Chemical compound CCCC[Si](CC)CCCC RSVCGWGXDUXRJI-UHFFFAOYSA-N 0.000 description 1
- XOTGQKPPHHXJCF-UHFFFAOYSA-N dibutyl(methyl)silane Chemical compound CCCC[SiH](C)CCCC XOTGQKPPHHXJCF-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- QWVFZGVJZUJZGG-UHFFFAOYSA-N diethyl(phenyl)silicon Chemical compound CC[Si](CC)C1=CC=CC=C1 QWVFZGVJZUJZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- QGBMSFLTRRZTGI-UHFFFAOYSA-N ethyl(dimethyl)silane Chemical compound CC[SiH](C)C QGBMSFLTRRZTGI-UHFFFAOYSA-N 0.000 description 1
- MGOBEGBHSBJTJR-UHFFFAOYSA-N ethyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](CC)C1=CC=CC=C1 MGOBEGBHSBJTJR-UHFFFAOYSA-N 0.000 description 1
- SCRLEJODSSWXCE-UHFFFAOYSA-N ethyl-methyl-phenylsilane Chemical compound CC[SiH](C)C1=CC=CC=C1 SCRLEJODSSWXCE-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical compound OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 description 1
- MHMUCYJKZUZMNJ-OWOJBTEDSA-N trans-3-chloroacrylic acid Chemical compound OC(=O)\C=C\Cl MHMUCYJKZUZMNJ-OWOJBTEDSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- WPPVEXTUHHUEIV-UHFFFAOYSA-N trifluorosilane Chemical compound F[SiH](F)F WPPVEXTUHHUEIV-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔発明の技術分野〕 本発明はシリル不飽和カルボキシレートの製造方法に
関する。更に詳しくは、不飽和カルボン酸とハイドロシ
ランとを反応させ、シリル不飽和カルボキシレートを収
率よく製造する方法に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a silyl unsaturated carboxylate. More specifically, it relates to a method for producing a silyl unsaturated carboxylate with a high yield by reacting an unsaturated carboxylic acid with hydrosilane.
シリル不飽和カルボキシレートの製造方法として、不
飽和カルボン酸の金属塩にクロロシランを反応させる方
法が知られている(D.N.Andreev.et al.,CA No.55 1533
2)。しかしこの反応では反応収率が低く、クロロシラ
ンが残存し、目的生成物の純度を下げるという欠点があ
った。As a method for producing a silyl unsaturated carboxylate, a method of reacting a metal salt of an unsaturated carboxylic acid with chlorosilane is known (DNAndreev. Et al., CA No. 55 1533.
2). However, this reaction has a drawback that the reaction yield is low, chlorosilane remains, and the purity of the target product is lowered.
また、不飽和カルボン酸とクロロシランをトリエチル
アミンのような塩酸捕獲剤の存在下に反応させて目的生
成物を得る方法もある。しかし、この方法では副生する
塩酸塩を除去しなければならず、工程が繁雑になり、濾
過工程の際に目的生成物が塩酸塩に吸着して著しく収率
が低下し、更に反応混合物を蒸留によって精製する場合
に塩酸塩が昇華・留出しやすく、目的生成物の純度を下
げるなどの欠点があった。There is also a method of obtaining an intended product by reacting an unsaturated carboxylic acid and chlorosilane in the presence of a hydrochloric acid scavenger such as triethylamine. However, in this method, the by-produced hydrochloride must be removed, the process becomes complicated, and the desired product is adsorbed on the hydrochloride during the filtration step, resulting in a significant decrease in yield. In the case of purification by distillation, there are drawbacks such that the hydrochloride salt is easily sublimated and distilled out, and the purity of the target product is lowered.
他方、カルボン酸とハイドロシランをPd,Ni,Rh触媒の
存在下で反応させて、シリルカルボキシレートを製造す
る方法が知られている(L.H.Sommer,J.E.Lyons,J.Am.Ch
em.Soc.,91,7061(1969))。しかしこの反応を不飽和
カルボン酸を用いて行うと、多量の飽和カルボン酸シリ
エステルが同時に生成する。特にRh触媒を使用した場合
は、カルボキシ基への付加反応も生じる。一方、触媒と
してPt触媒を使用した場合は不飽和カルボン酸の二重結
合への付加反応も生じる。特に不飽和カルボン酸が(メ
タ)アクリル酸の場合は、これらの副生成物の沸点が目
的生成物の沸点に近いため、蒸留による精製が難しく、
高純度のシリル(メタ)アクリレートを得るのは困難で
あった。On the other hand, a method for producing a silylcarboxylate by reacting a carboxylic acid and hydrosilane in the presence of Pd, Ni, Rh catalyst is known (LHSommer, JELyons, J.Am.Ch.
em.Soc., 91 , 7061 (1969)). However, when this reaction is carried out using an unsaturated carboxylic acid, a large amount of saturated carboxylic acid silyl ester is simultaneously produced. Especially when the Rh catalyst is used, an addition reaction to the carboxy group also occurs. On the other hand, when a Pt catalyst is used as the catalyst, an addition reaction of the unsaturated carboxylic acid to the double bond also occurs. Particularly when the unsaturated carboxylic acid is (meth) acrylic acid, the boiling points of these by-products are close to the boiling point of the target product, so that purification by distillation is difficult,
It was difficult to obtain high-purity silyl (meth) acrylate.
本発明は、好ましくない副生成物を生成することな
く、シリル不飽和カルボキシレートを収率良く製造する
方法の提供を目的とする。It is an object of the present invention to provide a method for producing a silyl unsaturated carboxylate in good yield without producing undesired by-products.
本発明者らは、かかる目的を達成するために鋭意検討
した結果、不飽和カルボン酸とハイドロシランとを、パ
ラジウム触媒と非プロトン性極性溶媒の存在下に反応さ
せると、不飽和カルボン酸の不飽和基の還元反応を伴う
ことなく、シリル不飽和カルボキシレートを高純度で収
率良く製造できることを見出し、本発明を成すに至っ
た。The present inventors have conducted extensive studies to achieve such an object, and as a result, when an unsaturated carboxylic acid and hydrosilane were reacted in the presence of a palladium catalyst and an aprotic polar solvent, the unsaturated carboxylic acid The present inventors have found that a silyl unsaturated carboxylate can be produced with a high purity and a high yield without accompanying a reduction reaction of a saturated group, and have completed the present invention.
即ち本発明は、一般式 (式中、R1,R2,R3は水素原子、ハロゲン原子又は置換も
しくは非置換の1価の炭化水素基を表す) で示される不飽和カルボン酸と、一般式 (式中、R4,R5,R6はアルコキシ基又は置換もしくは非置
換の1価炭化水素基を表す) で示されるハイドロシランとを、パラジウム触媒及び非
プロトン性極性溶媒の存在下に反応させることを特徴と
する一般式 (式中、R1〜R6は前述の通り) で示されるシリル不飽和カルボキシレートの製造方法に
関する。That is, the present invention has the general formula (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group), and an unsaturated carboxylic acid represented by the general formula (Wherein R 4 , R 5 and R 6 represent an alkoxy group or a substituted or unsubstituted monovalent hydrocarbon group) and are reacted with a hydrosilane represented by the formula (1) in the presence of a palladium catalyst and an aprotic polar solvent. General formula characterized by (In the formula, R 1 to R 6 are as described above) The present invention relates to a method for producing a silyl unsaturated carboxylate.
本発明に使用される不飽和カルボン酸(1)におい
て、R1,R2,R3は水素原子、ハロゲン原子又は置換もしく
は非置換の1価炭化水素基を表す。例えば、R1として
は、水素原子;メチル基、エチル基、プロピル基、ブチ
ル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル
基、ノニル基、デシル基、ドデシル基のようなアルキル
基;シクロペンチル基、シクロヘキシル基のようなシク
ロアルキル基;2−フェニルエチル基、2−フェニルプロ
ピル基のようなアラルキル基;フェニル基、トリル基の
ようなアリール基;カルボキシル基及びこれらの1価炭
化水素基の炭素原子に結合した水素原子が部分的にハロ
ゲン原子、アミノ基、シアノ基、アルコキシ基、水酸基
などで置換されたクロロメチル基、クロロフェニル基、
3,3,3−トリフルオロプロピル基、アミノエチル基、シ
アノエチル基、o−メトキシフェニル基、o−ヒドロキ
シフェニル基のような置換炭化水素基が例示される。こ
れらの中でも原料の入手が容易なことから、水素原子、
アルキル基、アラルキル基及びアリール基が好ましく、
特に水素原子、アルキル基が好ましい。R2としては、R1
と同様の置換基及び水素原子が例示され、同様に水素原
子、アルキル基、アラルキル基及びアリール基が好まし
く、特に水素原子、アルキル基が好ましい。またR3とし
ては、R1と同様の置換基及び水素原子が例示され、同様
に水素原子、アルキル基、アラルキル基及びアリール基
が好ましく、特に水素原子、アルキル基が好ましい。In the unsaturated carboxylic acid (1) used in the present invention, R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group. For example, R 1 is a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group or a dodecyl group; a cyclopentyl group , Cycloalkyl groups such as cyclohexyl groups; aralkyl groups such as 2-phenylethyl groups and 2-phenylpropyl groups; aryl groups such as phenyl groups and tolyl groups; carboxyl groups and carbons of these monovalent hydrocarbon groups A chloromethyl group in which a hydrogen atom bonded to an atom is partially substituted with a halogen atom, an amino group, a cyano group, an alkoxy group, a hydroxyl group, a chlorophenyl group,
Substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group, aminoethyl group, cyanoethyl group, o-methoxyphenyl group and o-hydroxyphenyl group are exemplified. Among these, because the raw materials are easily available, hydrogen atoms,
An alkyl group, an aralkyl group and an aryl group are preferable,
A hydrogen atom and an alkyl group are particularly preferable. R 2 is R 1
Substituents and hydrogen atoms similar to are exemplified, and hydrogen atom, alkyl group, aralkyl group and aryl group are also preferable, and hydrogen atom and alkyl group are particularly preferable. Examples of R 3 are the same substituents and hydrogen atoms as those of R 1 , hydrogen atom, alkyl group, aralkyl group and aryl group are preferable, and hydrogen atom and alkyl group are particularly preferable.
このような不飽和カルボン酸としては、アクリル酸、
メタクリル酸、2−エチルアクリル酸、クロトン酸、イ
ソクロトン酸、2−エチルクロトン酸、アンゲリカ酸、
2−クロロアクリル酸、3−クロロアクリル酸、ケイ皮
酸、α−メチルケイ皮酸、β−メチルケイ皮酸、o−メ
トキシケイ皮酸、マレイン酸、フマル酸などが例示され
るが、これらの中でも入手及び合成が容易なことから、
アクリル酸、メタクリル酸が好ましい。As such an unsaturated carboxylic acid, acrylic acid,
Methacrylic acid, 2-ethylacrylic acid, crotonic acid, isocrotonic acid, 2-ethylcrotonic acid, angelic acid,
2-chloroacrylic acid, 3-chloroacrylic acid, cinnamic acid, α-methylcinnamic acid, β-methylcinnamic acid, o-methoxycinnamic acid, maleic acid, fumaric acid and the like are exemplified, but among these, Because it is easy to obtain and synthesize,
Acrylic acid and methacrylic acid are preferred.
本発明において使用されるハイドロシラン(2)にお
いて、R4,R5,R6はアルコキシ基又は置換もしくは非置換
の1価炭化水素基を表す。例えばR4としては、メトキシ
基、エトキシ基、ブトキシ基、フェノキシ基などのアル
コキシ基;メチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基、ヘプチル基、オクチル
基、ノニル基、デシル基、ドデシル基のようなアルキル
基;シクロペンチル基、シクロヘキシル基のようなシク
ロアルキル基;2−フェニルエチル基、2−フェニルプロ
ピル基のようなアラルキル基;フェニル基、トリル基の
ようなアリール基及びこれらの1価炭化水素基の炭素原
子に結合した水素原子が部分的にハロゲン原子、アミノ
基、シアノ基、アルコキシ基、水酸基などで置換された
クロロメチル基、クロロフェニル基、3,3,3−トリフル
オロプロピル基、アミノエチル基、シアノエチル基、o
−メトキシフェニル基、o−ヒドロキシフェニル基のよ
うな置換炭化水素基が例示される。これらの中でも原料
の入手及び合成が容易なことから、アルキル基及びアリ
ール基が好ましく、特にメチル基、エチル基、ブチル基
及びフェニル基が好ましい。R5としてはR4と同様の置換
基が例示され、同様にアルキル基及びアリール基が好ま
しく、特にメチル基、エチル基、ブチル基及びフェニル
基が好ましい。またR6としてはR4と同様の置換基が例示
され、同様にアルキル基及びアリール基が好ましく、特
にメチル基、エチル基、ブチル基及びフェニル基が好ま
しい。In the hydrosilane (2) used in the present invention, R 4 , R 5 and R 6 represent an alkoxy group or a substituted or unsubstituted monovalent hydrocarbon group. For example, R 4 is an alkoxy group such as methoxy group, ethoxy group, butoxy group, phenoxy group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Group, alkyl group such as dodecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aralkyl group such as 2-phenylethyl group and 2-phenylpropyl group; aryl group such as phenyl group and tolyl group, and A chloromethyl group, a chlorophenyl group, 3,3,3-, in which a hydrogen atom bonded to a carbon atom of these monovalent hydrocarbon groups is partially substituted with a halogen atom, an amino group, a cyano group, an alkoxy group, a hydroxyl group or the like. Trifluoropropyl group, aminoethyl group, cyanoethyl group, o
Substituted hydrocarbon groups such as -methoxyphenyl group and o-hydroxyphenyl group are exemplified. Among these, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a butyl group, and a phenyl group are particularly preferable because the raw materials are easily available and can be synthesized. Examples of R 5 include the same substituents as R 4, and similarly, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a butyl group and a phenyl group are particularly preferable. Examples of R 6 include the same substituents as R 4, and similarly, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a butyl group and a phenyl group are particularly preferable.
このようなハイドロシランとしては、トリメチルシラ
ン、トリエチルシラン、トリブチルシラン、トリフェニ
ルシラン、メチルジエチルシラン、ジメチルエチルシラ
ン、メチルジブチルシラン、ジメチルブチルシラン、エ
チルジブチルシラン、ジエチルブチルシラン、メチルジ
フェニルシラン、ジメチルフェニルシラン、エチルジフ
ェニルシラン、ジエチルフェニルシラン、ブチルジフェ
ニルシラン、ジブチルフェニルシラン、メチルエチルブ
チルシラン、メチルエチルフェニルシラン、メチルブチ
ルフェニルシラン、エチルブチルフェニルシラン、メチ
ルジエトキシシラン、ジメチルエトキシシランなどが例
示されるが、これらの中でも入手及び合成が容易なこと
から、トリメチルシラン、トリエチルシラン、トリブチ
ルシラン及びトリフェニルシランが好ましい。Such hydrosilanes include trimethylsilane, triethylsilane, tributylsilane, triphenylsilane, methyldiethylsilane, dimethylethylsilane, methyldibutylsilane, dimethylbutylsilane, ethyldibutylsilane, diethylbutylsilane, methyldiphenylsilane, dimethyl. Examples include phenylsilane, ethyldiphenylsilane, diethylphenylsilane, butyldiphenylsilane, dibutylphenylsilane, methylethylbutylsilane, methylethylphenylsilane, methylbutylphenylsilane, ethylbutylphenylsilane, methyldiethoxysilane, and dimethylethoxysilane. However, among these, trimethylsilane, triethylsilane, tributylsilane, and trifluorosilane are easy to obtain and synthesize. Nirushiran is preferable.
本発明において使用されるパラジウム触媒としては、
パラジウム金属の配位化合物、パラジウム金属粉末、炭
素上に担持されたパラジウム金属及びパラジウム塩など
があげられ、配位化合物におけるパラジウムはいかなる
原子価を有していてもよい。これらの触媒としては、Pd
Cl2,PdCl2(PPh3)2,Pd(OCOCH3)2,PdCl2(PhCN)2の
ような均一系触媒、Pd−Cのような不均一系触媒などが
例示されるが、これらの中でも回収、再生が可能な点か
ら、Pd−Cが好ましい。The palladium catalyst used in the present invention includes
Examples thereof include a coordination compound of palladium metal, palladium metal powder, palladium metal supported on carbon and a palladium salt, and palladium in the coordination compound may have any valence. These catalysts include Pd
Examples are Cl 2 , PdCl 2 (PPh 3 ) 2 , Pd (OCOCH 3 ) 2 , PdCl 2 (PhCN) 2 homogeneous catalysts and Pd-C heterogeneous catalysts. Among them, Pd-C is preferable because it can be recovered and regenerated.
パラジウム触媒の使用量は特に制限されず、原料の種
類、反応温度、反応時間などを考慮して変えることがで
きるが、反応性、経済性の点からハイドロシランに対し
て100〜300ppmが好ましい。The amount of the palladium catalyst used is not particularly limited and can be changed in consideration of the type of raw material, the reaction temperature, the reaction time, etc., but from the viewpoint of reactivity and economical efficiency, it is preferably 100 to 300 ppm relative to the hydrosilane.
本発明において使用される非プロトン性極性溶媒は本
発明の特徴を成す成分であり、前記パラジウム触媒と組
み合わせることにより優れた効果を示す。非プロトン性
極性溶媒としては、ジメチルスルホキシド(DMSO)、N,
N−ジメチルホルムアミド(DMF)、ヘキサメチルホスホ
ルアミド(HMPA)、ニトロメタン、N−メチルピロリド
ン、アセトニトリル、アセトンなどが例示され、これら
のうちのいくつかを混合して使用してもよい。これらの
中でも優れた効果を示すことなどから、N,N−ジメチル
ホルムアミド、ジメチルスルホキシド、ヘキサメチルホ
スホルアミドが好ましい。The aprotic polar solvent used in the present invention is a component that characterizes the present invention, and exhibits excellent effects when combined with the palladium catalyst. As the aprotic polar solvent, dimethyl sulfoxide (DMSO), N,
N-dimethylformamide (DMF), hexamethylphosphoramide (HMPA), nitromethane, N-methylpyrrolidone, acetonitrile, acetone and the like are exemplified, and some of them may be used as a mixture. Among these, N, N-dimethylformamide, dimethylsulfoxide, and hexamethylphosphoramide are preferable because they exhibit excellent effects.
反応温度の制御、原料の溶解などのために、他の溶媒
を併用して反応溶媒とすることは可能であり、そのよう
な溶媒としては、例えばベンゼン、トルエン、キシレ
ン、n−ヘキサン、シクロヘキサンなどが挙げられる
が、反応溶媒中に非プロトン性極性溶媒を20重量%以上
含有していることが好ましい。In order to control the reaction temperature, dissolve the raw materials and the like, it is possible to use other solvents together as a reaction solvent, and examples of such a solvent include benzene, toluene, xylene, n-hexane, cyclohexane and the like. However, it is preferable that the reaction solvent contains 20% by weight or more of an aprotic polar solvent.
反応温度は40〜160℃、好ましくは80〜120℃の範囲で
ある。この温度範囲内で不飽和カルボン酸をハイドロシ
ランに対して好ましくは当量(モル)以上、2倍当量
(モル)以下、更に好ましくは1.3倍当量(モル)以
上、1.8倍当量(モル)以下反応させることにより、副
生成物の発生を抑え、収率良く目的生成物を製造するこ
とができる。反応生成物からは、通常の精製方法、例え
ば蒸留などにより純度の高い目的生成物を得ることがで
きる。The reaction temperature is in the range of 40 to 160 ° C, preferably 80 to 120 ° C. Within this temperature range, the unsaturated carboxylic acid is preferably equivalent to (molar) or more and 2 times equivalent (mol) or less, more preferably 1.3 times equivalent (mol) or more and 1.8 times equivalent (mol) or less with respect to the hydrosilane. By so doing, the generation of by-products can be suppressed and the target product can be produced in good yield. From the reaction product, a highly purified target product can be obtained by a conventional purification method such as distillation.
また、本発明の製造方法においては、原料の不飽和カ
ルボン酸や、生成物の不飽和カルボキシレートの重合を
防止するために、酸素、ヒドロキノン、p−メトキシフ
ェノールなどの重合防止剤を添加することが好ましい。Further, in the production method of the present invention, a polymerization inhibitor such as oxygen, hydroquinone, or p-methoxyphenol is added in order to prevent polymerization of unsaturated carboxylic acid as a raw material or unsaturated carboxylate as a product. Is preferred.
本発明の製造方法によりHClのような好ましくない副
生成物を発生することなく、目的とするシリル不飽和カ
ルボキシレートを収率よく製造することができる。また
副生成物の濾過工程なども不要であり、工程が簡略とな
り、また、不均一系の触媒を使用した場合は、回収、再
生が可能となり、効率の良い触媒の使用ができる。ま
た、加水分解性の高いクロロシランの代わりにハイドロ
シランを使用するとができ、原料の取り扱いが容易とな
る。According to the production method of the present invention, the desired silyl unsaturated carboxylate can be produced in good yield without generating an undesirable by-product such as HCl. Further, the step of filtering the by-product is not necessary, the process is simplified, and when a heterogeneous catalyst is used, it can be recovered and regenerated, and the catalyst can be used efficiently. Further, hydrosilane can be used in place of chlorosilane having high hydrolyzability, and the raw material can be easily handled.
以下に実施例と比較例を示し、本発明を具体的に説明
する。尚、例中、%は重量%を示す。Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples,% means% by weight.
実施例1 温度計、還流冷却器を取り付けたフラスコに、N,N−
ジメチルホルムアミド(DMF)870g、パラジウムを0.5%
含有するPd−C触媒40gを入れ、撹拌しながら110℃まで
加熱した。その後メタクリル酸560g、トリブチルシラン
1000g、p−メトキシフェノール2gの混合物を添加し
た。反応中、水素が発生し、発熱が観察されるので反応
温度を110〜120℃に保って4時間撹拌した。Example 1 A flask equipped with a thermometer and a reflux condenser was charged with N, N-
870g of dimethylformamide (DMF), 0.5% of palladium
40 g of the Pd-C catalyst contained therein was added and heated to 110 ° C with stirring. Then 560 g of methacrylic acid, tributylsilane
A mixture of 1000 g and 2 g of p-methoxyphenol was added. During the reaction, hydrogen was generated and an exotherm was observed, so the reaction temperature was kept at 110 to 120 ° C. and the mixture was stirred for 4 hours.
水素の発生が止まり反応が終了した後、室温まで冷却
し、Pd−C触媒を濾別した。次いで減圧蒸留することに
よって115〜117℃/3Torrの留分を1180g得た。この留分
についてGC−Mass,NMR,IR分析を行ったところ、トリブ
チルシリルメタクリレートが91%及びその不飽和結合の
還元体であるトリブチルシリルイソブタノエートが8%
存在することがわかった。トリブチルシリルメタクリレ
ートの単離収率は83%であった。After the generation of hydrogen stopped and the reaction was completed, it was cooled to room temperature and the Pd-C catalyst was filtered off. Then, it was distilled under reduced pressure to obtain 1180 g of a fraction of 115 to 117 ° C./3 Torr. GC-Mass, NMR, and IR analyzes of this fraction revealed that 91% tributylsilylmethacrylate and 8% tributylsilylisobutanoate, which is the reduction product of the unsaturated bond, were obtained.
It turned out to exist. The isolated yield of tributylsilyl methacrylate was 83%.
実施例2 温度計、還流冷却器を取り付けたフラスコに、N,N−
ジメチルホルムアミド(DMF)870g、パラジウムを0.5%
含有するPd−C触媒52gを入れ、撹拌しながら110℃まで
加熱した。その後アクリル酸420g、トリフェニルシラン
1300g、p−メトキシフェノール2gの混合物を添加し
た。反応中、水素が発生し、発熱が観察されるので反応
温度を110〜120℃に保って4時間撹拌した。Example 2 A flask equipped with a thermometer and a reflux condenser was charged with N, N-
870g of dimethylformamide (DMF), 0.5% of palladium
52 g of the Pd-C catalyst contained therein was added and heated to 110 ° C. with stirring. After that, 420g acrylic acid, triphenylsilane
A mixture of 1300 g and 2 g of p-methoxyphenol was added. During the reaction, hydrogen was generated and an exotherm was observed, so the reaction temperature was kept at 110 to 120 ° C. and the mixture was stirred for 4 hours.
水素の発生が止まり反応が終了した後、室温まで冷却
し、Pd−C触媒を濾別した。次いで減圧下で溶媒を除去
し、更にn−ヘキサンで洗浄することで固体分を1240g
得た。この固体分について四塩化炭素に溶解させ、GC,N
MR,IR分析を行ったところ、トリフェニルシリルアクリ
レートが90%及びその不飽和結合の還元体であるトリフ
ェニルシリルプロピオネートが4%、またトリフェニル
シラノールが4%存在することがわかった。トリフェニ
ルシリルアクリレートの単離収率は79%であった。After the generation of hydrogen stopped and the reaction was completed, it was cooled to room temperature and the Pd-C catalyst was filtered off. Then, the solvent was removed under reduced pressure, and the solid content was washed with n-hexane to obtain 1240 g of solid content.
Obtained. This solid content was dissolved in carbon tetrachloride, and GC, N
MR and IR analyzes revealed that 90% of triphenylsilyl acrylate, 4% of triphenylsilylpropionate, which is a reduction product of its unsaturated bond, and 4% of triphenylsilanol were present. The isolated yield of triphenylsilyl acrylate was 79%.
実施例3 反応溶媒として実施例1で用いたDMF870gの代わりに
トルエン720gとDMF150gの混合物を用いた以外は実施例
1と同様に反応、蒸留を行ったところ反応生成物が1120
g得られ、トリブチルシリルメタクリレートが68%、そ
の不飽和結合の還元体であるトリブチルシリルイソブタ
ノエートが32%存在することがわかった。Example 3 As a reaction solvent, instead of 870 g of DMF used in Example 1, a mixture of 720 g of toluene and 150 g of DMF was used.
It was found that 68% of tributylsilyl methacrylate and 32% of tributylsilyl isobutanoate, which is a reduction product of the unsaturated bond, were present.
比較例1 反応溶媒として実施例1で用いたDMF870gの代わり
に、トルエン870gを用いた以外は実施例1と同様に反応
を行ったところ10時間後でも反応は進行せず、反応混合
物をガスクロマトグラフィー(GC)で分析したところ、
原料であるトリブチルシランが残存していた。Comparative Example 1 The reaction was performed in the same manner as in Example 1 except that 870 g of toluene was used instead of 870 g of DMF used in Example 1 as a reaction solvent, and the reaction did not proceed even after 10 hours, and the reaction mixture was subjected to gas chromatography. When analyzed by chromatography (GC),
The starting material, tributylsilane, remained.
比較例2 温度計、還流冷却器を取り付けたフラスコに、トルエ
ン750g、トリエチルアミン505g、メタクリル酸560g、p
−メトキシフェノール2gを仕込み、撹拌、混合した。こ
の後トリブチルクロロシラン1172gを滴下開始した。反
応中、塩酸塩の生成及び発熱が観察され、反応温度を50
〜60℃に保って滴下、撹拌を続け、約2時間かけて滴下
を終了した。反応混合物をGCで分析したところ、原料の
トリブチルクロロシランのピークは消失していた。Comparative Example 2 To a flask equipped with a thermometer and a reflux condenser, 750 g of toluene, 505 g of triethylamine, 560 g of methacrylic acid, p
-Methoxyphenol 2g was prepared, stirred and mixed. After that, 1172 g of tributylchlorosilane was added dropwise. During the reaction, formation of a hydrochloride and an exotherm were observed, and the reaction temperature was 50
The dropping was continued while maintaining the temperature at -60 ° C, and the dropping was completed over about 2 hours. When the reaction mixture was analyzed by GC, the peak of the starting material tributylchlorosilane had disappeared.
室温まで冷却してから塩酸塩を濾別し、続いて減圧蒸
留することにより、115〜117℃/3Torrの留分を866g得
た。単離収率は61%であった。蒸留して得た留分を冷却
すると、塩酸塩の析出が見られた。After cooling to room temperature, the hydrochloride was filtered off, followed by vacuum distillation to obtain 866 g of a fraction of 115 to 117 ° C./3 Torr. The isolation yield was 61%. When the fraction obtained by distillation was cooled, precipitation of hydrochloride was observed.
比較例3 触媒として実施例1で用いたPd−C触媒40gの代わり
に塩化白金酸(H2PtCl6)0.42gを用いた以外は実施例1
と同様に反応を行った。110〜120℃で4時間撹拌したと
ころ、原料のトリブチルシランの残存がGCで確認された
ので、更に2時間撹拌してトリブチルシランの消失を確
認して反応を終了させた。Comparative Example 3 Example 1 was repeated except that 0.42 g of chloroplatinic acid (H 2 PtCl 6 ) was used instead of 40 g of the Pd—C catalyst used in Example 1 as the catalyst.
The reaction was performed in the same manner as in. After stirring at 110 to 120 ° C. for 4 hours, residual tributylsilane as a raw material was confirmed by GC. Therefore, stirring was continued for 2 hours, and disappearance of tributylsilane was confirmed, and the reaction was terminated.
その後、減圧蒸留を行い、114〜117℃/3Torrの留分を
1130g得た。この留分についてGC−Mass,NMR,IR分析を行
ったところ、トリブチルシリルメタクリレートが48%、
その不飽和結合の還元体であるトリブチルシリルイソブ
タノエートが50%存在することがわかった。After that, vacuum distillation is performed, and the fraction of 114-117 ° C / 3 Torr is obtained.
1130 g was obtained. GC-Mass, NMR, IR analysis of this fraction showed that tributylsilyl methacrylate was 48%,
It was found that tributylsilylisobutanoate, which is a reduction product of the unsaturated bond, was present in 50%.
Claims (3)
しくは非置換の1価の炭化水素基を表す) で示される不飽和カルボン酸と、一般式 (式中、R4,R5,R6はアルコキシ基又は置換もしくは非置
換の1価炭化水素基を表す) で示されるハイドロシランとを、パラジウム触媒及び非
プロトン性極性溶媒の存在下に反応させることを特徴と
する一般式 (式中、R1〜R6は前述の通り) で示されるシリル不飽和カルボキシレートの製造方法。1. A general formula (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group), and an unsaturated carboxylic acid represented by the general formula (Wherein R 4 , R 5 and R 6 represent an alkoxy group or a substituted or unsubstituted monovalent hydrocarbon group) and are reacted with a hydrosilane represented by the formula (1) in the presence of a palladium catalyst and an aprotic polar solvent. General formula characterized by (In the formula, R 1 to R 6 are as described above).
ミドである請求項1記載のシリル不飽和カルボキシレー
トの製造方法。2. The method for producing a silyl unsaturated carboxylate according to claim 1, wherein the aprotic polar solvent is dimethylformamide.
リル酸である請求項1記載のシリル不飽和カルボキシレ
ートの製造方法。3. The method for producing a silyl unsaturated carboxylate according to claim 1, wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2280255A JP2542117B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing silyl unsaturated carboxylate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2280255A JP2542117B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing silyl unsaturated carboxylate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04154790A JPH04154790A (en) | 1992-05-27 |
JP2542117B2 true JP2542117B2 (en) | 1996-10-09 |
Family
ID=17622450
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Application Number | Title | Priority Date | Filing Date |
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JP2280255A Expired - Fee Related JP2542117B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing silyl unsaturated carboxylate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2542117B2 (en) |
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1990
- 1990-10-17 JP JP2280255A patent/JP2542117B2/en not_active Expired - Fee Related
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JPH04154790A (en) | 1992-05-27 |
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